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    Please use this identifier to cite or link to this item: http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/32783

    Title: 亞硝/亞胺亞硝自由基及其金屬錯合物及氰基為架橋之镧系金屬錯合物之結構及磁性性質研究
    Other Titles: Structures and magnetic properties of imino/nitronyl nitroxide radicals and their metal complexes and cyano-bridged of lanthanide complexes.
    Authors: 林信宏;Lin, Hsin-huang
    Contributors: 淡江大學化學學系博士班
    魏和祥;Wei, Ho-hsiang
    Keywords: 金屬錯合物;亞硝自由基;镧系錯合物;晶體結構;磁性性質;Metal complexes;nitronyl nitroxide radicals;lanthanide complexes;crystal srtucrures;magnetic properties
    Date: 2005
    Issue Date: 2010-01-11 02:44:55 (UTC+8)
    Abstract: 本論文研究主題為探討自由基化合物及其金屬錯合物之磁性與構造關連性及異核镧系金屬錯合物的磁性性質。內容分為二大部份。
    第一部份為亞硝/亞胺亞硝自由基及其金屬磁構造關聯性的研究,在本論文裡一共合成了12個自由基配位子[NITpPy、NITmPy、NIT-tz、NIT-Ida、IM-Py、IM-mPy、NITpBA、IM-pBA、IM-oBA、NITmBA、NITpAH、IM-oPy]其中NITpPy、NITmPy、NITpBA、IM-pBA、NITmBA、NITpAH,有得到單晶構,而在其金屬錯合物方面一共得到17個錯合物,而它們的磁構造關聯性測量結構如下:(1). NITpPy、IM-pBA 分子間有微弱的鐵磁性偶合作用,其餘則為反鐵磁性偶合作用。(2).在錯合物方面其中[Mn(NITpPy)2(N(CN)2)2(H2O)2] [Cu(CHCl2COO)2(NITmPy)2(H2O)2]、[Gd2(NITpPy)4(N(CN)2)4(OH)2] [Mn(NITpPy)4(N3)2]、[Cu(hfac)2(NITmPy)2]、 [Cu(NIT-tz)2(N3)2]、 [Ag(NITpBA)]、 [Ag(IM-mPy)(NO3)]、[Ag1.5(IM-oBA)(0.5NO3)]等九個錯合物為鐵磁性偶合作用,而[Mn(NIT-Ida)2Cl2], [Ni(NIT-tz)2Cl2] [Co(NITpPy)2(N(CN)2)2(H2O)2]、 [Mn(NIT-tz)(N(CN)2)2]、 [Co(NITpPy)4(N3)2]、 [Ag(IM-Py)(NO3)]和[Ni(NITpPy)4(N3)2]則為反鐵磁性偶合作用,此外透過N(CN)2-為架橋基的錯合物其分子內金屬的磁偶合作用相當的微弱。(3). Pt(Ⅱ)的錯合物[Pt(II)(IM-oPy)Cl2]由於其配位環境與抗癌藥物相當類似,因此嘗試將此錯合物和DNA作用,以進一步了解其反應機制。
    在第二部份一共合成11個異核(Ln3+)镧系金屬Fe(CN)63-錯合物物[Ln(dmf)4(H2O)3Fe(CN)6]•2H2O, ( Ln = Ce、Pr、Nd、Sm、Eu、Gd、
    Tb、Dy、Ho、Er、Tm 、Yb )及2個異核(Ln3+)镧系金屬Co(CN)63-錯合物[Ln(dmf)4(H2O)3Co(CN)6]•H2O ( Ln = Pr、Er )和3個一維及1個三維結構錯合物其分子式如下:
    [Ln(dmf)4(H2O)2Cr(CN)6]•H2O ( Ln = Pr、Sm)

    以上總共17個镧系金屬錯合物的磁構造關聯性,其分子內的鐵磁或反鐵磁性行為,則伴隨著镧系金屬離子4f 軌域上電子數不同而有不同的磁性表現。
    The present thesis has been divided into two parts:

    PartⅠ: Preparations, structures and magnetic properties of the free radicals of nitronyl nitroxide and imino nitroxide and their metal complexes have been reported. The temperature dependence of magnetic properties of these free radicals and their metal complexes are measured, the magneto-structural correlations also have been discussed . At first, twelve nitronyl/imino nitroxide derivatives are prepared, in which the crystal structures of the free radical ligands of NITpPy、NITmPy、NITpBA、IM-pBA、NITmBA、NITpAH have determined by X-ray diffraction. The temperature dependence of the magnetic susceptibility measurements of these twelve radical ligands and their seven-teen metal complexes are measured. The results are described at the followings: (1) only NITpPy and IM-pBA exhibit a weak ferromagnetic coupling and the others are all in antiferromagnetic coupling. (2) nine complexes of [Cu(CHCl2COO)2(NITmPy)2(H2O)2], [Mn(NITpPy)2(N(CN)2)2(H2O)2], [Mn(NITpPy)4(N3)2], [Cu(hfac)2(NITmPy)2], [Cu(NIT-tz)2(N3)2], [Gd2(NITpPy)4(N(CN)2)4(OH)2], [Ag(NITpBA)], [Ag(IM-mPy)(NO3)], [Ag1.5(IM-oBA)(0.5NO3)] exhibit ferromagnetic coupling, whereas [Co(NITpPy)2(N(CN)2)2(H2O)2], [Mn(NIT-Ida)2Cl2], [Ni(NIT-tz)2Cl2], [Mn(NIT-tz)(N(CN)2)2], [Co(NITpPy)4(N3)2], [Ag(IM-Py)(NO3)] and [Ni(NITpPy)4(N3)2] are antiferromagnetic coupling. The magnetic exchange mechanism for these complexes have been discussed. In addition, the result also show that magnetic interaction through the N(CN)2- bridge are very weak. (3) [Pt(II)(IM-oPy)Cl2] coordinate environment is quite similar anticancer drug, so that the interaction with Ф174 double stranded DNA has been studied to understand its response mechanism.

    Part II : eleven discrete heterdinuclear [Ln(dmf)4(H2O)3Fe(CN)6]•H2O
    ( Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb ),
    two [Ln(dmf)4(H2O)3Co(CN)6]•H2O ( Ln = Pr and Er ), 1-D
    [Ln(dmf)4(H2O)2Cr(CN)6]•H2O ( Ln = Pr and Sm),
    [Gd(o-phen)(dmf)2(H2O)2-Fe(CN)6]•3H2O, and 3-D
    [DyFe(CN)6(H2O)2]•H2O complexes with Ln-NC-M(3d) have been prepared and structural characterized. The magnetic properties for these seven teen complexes have been determined by temperature dependence of magnetic susceptibility measurements. The intramolecular anti- and ferromagnetic couplings between Ln-NC-M(3d) are dependence of electron configuration of 4 fn.
    Appears in Collections:[化學學系暨研究所] 學位論文

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